Chem Topic 4

TOPIC 4
ELECTROCHEMISTRY
COMPILED BY :
HAZWANEE BINTI OSMAN
TS. NAJWA RAWAIDA BINTI AHMAD @ AHMAD FAUZI
CONTENT
4.1 Redox Reactions

4.2 Galvanic Cell
4.3 Standard Electrode Potential
4.4 Non-standard Cell Potential
4.5 Electrolytic Cell and Its Applications
4.1 REDOX REACTIONS
LEARNING OBJECTIVES
Student should be able to:

• Explain the characteristics of redox reaction in terms of electron transfer
and oxidation number changes
• Write a balance ionic half-equation and net ionic equation using the method
of half-equation in acidic and basic solutions.
4.1 REDOX REACTIONS
4.1.1 Redox Reaction and Oxidation State

Electrochemistry is the study of redox reaction that produce or require an
electric current
 Redox reactions are involved the transfer of one or more electrons from
one chemical species to another called reduction-oxidation (oxidation
state of atoms are changed)
 Reducing agent undergoes oxidation (loss electrons) – increase in
oxidation state
 Oxidizing agent undergoes reduction (gain electrons) – decrease in
oxidation state
OILRIG
Oxidation is
Loss Reduction
is Gain
4.1 REDOX REACTIONS

Spontaneous Redox Reaction Non-spontaneous Redox Reaction
 Take place in voltaic cell  In electrolytic cell by addition of

(electrochemical cell) electric energy (battery)
 Conversion of:-  Conversion of:-
Chemical Electrical Electrical Chemical

Energy Energy Energy Energy
 Eg: galvanic cell  Eg: electrolysis
Picture taken from https://chem.libretexts.org/Textbook_Maps/Analytical_Chemistry/Supplemental_Modules_(Analytical_Chemistry)/Electrochemistry/Voltaic_Cells and https://byjus.com/physics/electrolysis-and-electroplating

4.1 REDOX REACTIONS

OXIDATION REDUCTION
 An element loses electron  An element gains electron
 Oxidation number of element  Oxidation number of element

increases decreases
 The element is known as reducing  The element is known as oxidizing

agent agent
 A compound adds oxygen &  A compound loses oxygen &

loses hydrogen gains hydrogen
 A half-equation has electrons as  A half-equation has electrons as

product reactants
 Eg: Cr2+(aq) Cr3+(aq)+ e-  Eg: Ag+(aq) + e-  Ag (s)

4.1 REDOX REACTIONS
 Oxidation numbers also called as oxidation state.

 Represent the number of electrons that an atom can gain, lose or shared
when chemically bonding with an atom of another element.
 It is actually a positive or negative number assigned to an atom or ion to
show how it is bonded to another element in a substance.
 The oxidation number is assigned according to a set of rules.
4.1 REDOX REACTIONS
The 8 rules in assigning the oxidation states
Rule (1):
The oxidation number of any free element is 0.
Na = 0 and Cl2 = 0 [ 2Na(s) + Cl2(g) → 2NaCl(s) ]
Rule (2):
The oxidation number for any simple, monoatomic ion is equal to the charge.
Na+ = +1 and Cl- = −1 [ NaCl ]
4.1 REDOX REACTIONS
Rule (3):
a) The sum of all oxidation numbers of the atoms in a neutral molecule must
equal to zero.
Na+ = +1 and Cl- = −1 [ NaCl, (+1) + (−1) = 0 ]
b) The sum of all the oxidation numbers in a polyatomic ion must equal to the
charge on the ion.
N = +5 and O = −2 [ NO3–, (+5) + 3(−2) = −1 ]
Rule (4):
Group I metals have an oxidation state of +1 in all their compounds.
Na+ = +1 [ NaCl ]
4.1 REDOX REACTIONS
Rule (5):
Group II metals have an oxidation state of +2 in all their compounds
Mg2+ = +2 [ MgCl2 ]
Rule (6):
For hydrogen, assign the oxidation number as follows:
a) Hydrogen + non-metal  covalent hydride
The oxidation number of hydrogen in these covalent
hydride is +1
Examples: HCl, H2O, NH3, H2SO3, OH– and NH4+
4.1 REDOX REACTIONS
b) Hydrogen + metal → ionic hydride (a binary compound)

The oxidation number of hydrogen in these ionic hydrides
is –1.
Examples: LiH, NaH, KH, MgH2 and CaH2.
Rule (7):
For oxygen, assign the oxidation number as follows:
a) The oxidation number of O in oxides is –2.
Examples: Na2O, BaO, H2O, Al2O3, CO2, SO3, CO32–, SO42–
b) The oxidation number of O in peroxides (O22-), superoxides
(O2-) is –1.
Example: Na2O2, BaO2, H2O2.
4.1 REDOX REACTIONS
c) The oxidation number of Oxygen is +2 when combine with a

more electronegative atom (e.g. F atom ).
Example: F2O.
Rule(8):
For Group VII elements, assign the oxidation number as follows:
a) Fluorine has an oxidation number of –1 in all its compounds.
b) Other halogens (Cl, Br, and I) have oxidation numbers -1 when they occur as
halide ions in their compounds.
c) When combined with oxygen, for example in oxyanions:
HClO4, ClO3–, BrO3–, ClO2– and IO3–,
the oxidation number of the halogen is positive.
EXAMPLE
What is the oxidation number for each kind of atom in the following ions and
compounds?
a) Na2SO4
b) (NH4)2S
SOLUTION
Use the set of rules you just learned to assign and calculate oxidation
numbers.
a) Na2SO4
 The oxidation number of each sodium ion, Na+, is the same as its ionic
charge, +1 (Rule 2).
 The sum of the oxidation numbers in the neutral compound to be 0 (Rule
3a),
 There are four oxygen atoms, and the oxidation number of each oxygen is
–2 (Rule 7a).
 2(1) + S + 4(-2) = 0
S+2–8=0
S = +6
 Therefore, the oxidation number of sulfur must be +6, because (2 × (+1)) +
(+6) + (4 × (–2)) = 0.
+1 ? –2 +1 +6 –2
Na2SO4 Na2SO4
b) (NH4)2S
Ammonium ions, NH4+, have an ionic charge of +1 (Rule 3b), so the sum of
the oxidation numbers of the atoms in the ammonium ion must be +1. Two
ammonium ions have a total charge of +2.
The oxidation number of hydrogen is +1 in this ion (Rule 6a). So, the
oxidation number of nitrogen must be –3.
 N + 4(+1) = +1
N = +1 – 4
= -3
Since the compound (NH4)2S is neutral, the sum of the oxidation numbers in
the neutral compound to be 0 (Rule 3a)
 2 ( -3 + 4(+1)) + S = 0
2 ( +1) + S = 0
S = -2
Therefore, sulfur must have a balancing oxidation number of –2, because
((2 ×(4× (+1)) + (–3 )) + (–2)) = 0 ? +1 –3 +1 –2
NH4 + (NH4)2S
? + 4(+1) = +1
–3 + 4(+1) = +1
CHECKPOINT 1
QUESTION 1
Consider the equation below:-
Fe2+ (aq) + MnO4- (aq)  Fe3+ (aq) + Mn2+ (aq)
i) Determine the oxidation numbers of Mn in MnO4-

ii) State which element undergoes oxidation and reduction and justify.
iii) Identify oxidizing agent and reducing agent
4.1 REDOX REACTIONS
4.1.2 Balancing Redox Equations
 Many redox reactions take place in aqueous solution.

 The oxidation and reduction processes are divided into two equations
called half-equation.
 The half-equation are balanced separately, then combined into the fully
balanced net ionic (overall) equation.
 In this method, the reaction is separated into two half-equation; oxidation
and reduction.
 Each half-equation consist of:
 electrons on the product side of the oxidation half-equation (loss of
electrons)
 electrons on the reactant side of the reduction half-equation (gain of
electrons)
EXAMPLE
Balance the following redox equation:

Fe3+ (aq) + Sn2+ (aq) → Fe2+(aq) + Sn4+ (aq)
SOLUTION
This redox equation consists of two half-equations:

Sn2+ → Sn4+ oxidation (2+ 4+)
Fe3+ → Fe2+ reduction (3+ 2+)
Each half-equation is balanced for its atoms first, then its charge.
Sn2+ → Sn4+ + 2e- oxidation
left right
+2 (+4) + (-2) = +2 The charge is balanced
Fe3+ + e- → Fe2+ reduction
right
+3 + (-1) =+2
left The charge is balanced
+2
One or both are multiplied by some integer to make the number of electrons
gained and lost equal.
[Fe3+ + e- → Fe2+ ]x 2 reduction
2Fe3+ + 2e- → 2Fe2+ reduction
Then balance the number of electrons in the two half-equations and add them
together to obtain a balanced overall equation.
2Fe3+ + 2e- → 2Fe2+ reduction
Sn2+ (aq) + 2Fe3+ (aq) → Sn4+(aq) + 2Fe2+ (aq)
Note: all steps above is called as skeleton equation

4.1 REDOX REACTIONS
Redox reactions in acidic and basic solution:

 H+ or OH- ions play an important role in many redox reactions.
 The product of a redox reaction is based on the acidity of the solution.
 Slightly different methods are used to balance redox reactions in acidic and
basic solutions.
4.1 REDOX REACTIONS
Balancing oxidation-reduction equations in acidic medium:
Consider this equation
Zn(s ) + NO3 − (aq ) → Zn2+ (aq ) + NH4+ (aq )
Step 1:
Determine oxidation number for each atoms in the substance
0 +5 +2 –3
4.1 REDOX REACTIONS
Step 2:
0 +5 +2 –3
Separate equation into two half-equation. Note that zinc is oxidized, and
nitrogen is reduced
Zn(s ) → Zn2+ (aq ) oxidation

NO3 − (aq ) → NH4+ (aq ) reduction
Step 3:
Oxidation half-equation
Add electron on the right-hand side to balance the charge
Zn(s ) → Zn2+ (aq ) + 2e − (oxidation half-reaction)

4.1 REDOX REACTIONS
Step 3:
Reduction half-equation
NO3-(aq)  NH4+ (aq)
a. Balance other atoms first (balance N atoms first)

b. Balance O atoms by adding H2O to the side of the equation that needs
oxygen
NO3-(aq)  NH4+ (aq) + 3H2O (l)
c. Balance H atoms by adding H+ to the side of equation

that needs hydrogen
NO3-(aq) + 10 H+ (aq)  NH4+ (aq) + 3H2O (l)
4.1 REDOX REACTIONS
Step 4:
Balance the charge by adding electrons (e-) to the reactant side of the equation
(reduction)
NO3-(aq) + 10 H+ (aq)  NH4+ (aq) + 3H2O (l)
-1 + 10 = +1 + 0
+9 = +1
So, the left-hand side should add 8 electrons to make it balance with the right-
hand side
NO3-(aq) + 10 H+ (aq) + 8e-  NH4+ (aq) + 3H2O (l)
.
4.1 REDOX REACTIONS
Step 5:
Combine the two half-equations.
Zn (s)  Zn2+ (aq) + 2e- oxidation
NO3-(aq) + 10 H+ (aq) + 8e-  NH4+ (aq) + 3H2O (l) reduction
a. Multiply each half-equation by a factor so that each has the same

number of electrons.
4 x [Zn (s)  Zn2+ (aq) + 2e- ] oxidation
4Zn (s)  4Zn2+ (aq) + 8e- oxidation
4.1 REDOX REACTIONS
b. Add the two half-equation (the electrons should cancel each other).
c. Simplify the overall reaction by canceling species that occur on both
sides and reducing the coefficients to the smallest whole numbers.
d. Check that the equation is balanced

NO3-(aq) + 4Zn (s) + 10 H+ (aq)  NH4+ (aq) + 4Zn2+ (aq) + 3H2O (l)
Indicates the redox reaction

is in acidic medium
Note: electron should not appear in overall balanced equation
4.1 REDOX REACTIONS
Balancing oxidation-reduction equations in basic medium:
Consider the same equation;
Use the same steps as in acidic solution; from Step 1 to Step 3c.
4.1 REDOX REACTIONS
Step 3:
c. To balance H atoms, add H+ to other side of equation that needs
Hydrogen
NO3-(aq) + 10 H+ (aq)  NH4+ (aq) + 3H2O (l)
d. Note the number of H+ ions in the equation. Add this number of OH−
ions to both sides of the equation.
NO3-(aq)+ 10H+(aq) + 10OH-(aq)  NH4+ (aq) + 3H2O (l) + 10OH- (aq)
10H2O (l)
4.1 REDOX REACTIONS
e. Simplify the equation by noting that H+ and OH− react to form H2O.
Cancel water molecules that occur on both sides.
NO3-(aq)+ 10H+(aq) + 10OH- (aq)  NH4+ (aq) + 3H2O (l) + 10OH- (aq)
10H2O (l)
= 7H2O (l)
4.1 REDOX REACTIONS
Continue Step 4 and Step 5 as in acidic solution;

Step 4:
Balance the electric charge by adding electrons (e-) to the more positive side
of the equation
NO3-(aq) + 7H2O (l)  NH4+ (aq) + 10OH- (aq)
-1 + 0 = +1 + (-10)
-1 = -9
So, the left-hand side should add 8 electrons to make it balance with the right-
hand side
NO3-(aq) + 7H2O (l) + 8e-  NH4+ (aq) + 10OH- (aq)
4.1 REDOX REACTIONS
Step 5:
Combine the two half-equations.
Zn (s)  Zn2+ (aq) + 2e- oxidation
NO3-(aq) + 7H2O (l) + 8e-  NH4+ (aq) + 10OH- (aq) reduction
a. Multiply each half-equation by a factor so that each has the same

number of electrons.
4 x [Zn (s)  Zn2+ (aq) + 2e- ] oxidation
4.1 REDOX REACTIONS
b. Add the two half-equations (the electrons should cancel each other).
c. Simplify the overall reaction by canceling species that occur on both
sides and reducing the coefficients to the smallest whole numbers.
d. Check that the equation is balanced.

NO3-(aq) + 7H2O (l) + 4Zn (s)  NH4+ (aq) + 4Zn2+ (aq) + 10OH- (aq)
Indicates the redox reaction is

in basic medium

4.1 REDOX REACTIONS
OR,
To simplify the steps for basic solution, follow Step 1 until Step 5 for acidic
solution,
NO3-(aq) + 4Zn (s) + 10 H+ (aq)  NH4+ (aq) + 4Zn2+ (aq) + 3H2O (l)
Indicates the redox reaction

is in acidic solution
Since there are 10 H+, add this number of OH− ions to both sides of the
equation
NO3-(aq) + 4Zn (s) + 10 H+ (aq) + 10 OH− (aq)

 NH4+ (aq) + 4Zn2+ (aq) + 3H2O (l) + 10 OH− (aq)
4.1 REDOX REACTIONS
Simplify the equation by noting that H+ and OH− react to form H2O. Cancel
water molecules that occur on both sides.
10H2O (l) = 7H2O (l)
NO3-(aq) + 4Zn (s) + 10 H+ (aq) + 10 OH− (aq)

 NH4+ (aq) + 4Zn2+ (aq) + 3H2O (l) + 10 OH− (aq)
NO3-(aq) + 7H2O (l) + 4Zn (s)  NH4+ (aq) + 4Zn2+ (aq) + 10OH- (aq)
Indicates the redox reaction is

in basic solution

CHECKPOINT 2
Write a balanced net ionic (overall) equation in an acidic solution.
H2C2O4 (s) + MnO4¯ (aq)  CO2 (g) + Mn2+ (aq)

CHECKPOINT 3
Write a balanced net ionic equation showing the oxidation of Fe2+ ions by
dichromate ions (Cr2O72-) in a basic medium.
Fe2+ + Cr2O72-  Fe3+ + Cr3+

4.2 GALVANIC CELL
LEARNING OBJECTIVES

• Sketch and describe the components and operation of the galvanic cell
• Write a cell notation of the galvanic cell
• Construct redox equation from cell notation or from a given diagram of
galvanic cell or vice versa.
4.2 GALVANIC CELL
Setting up a galvanic cell
 A potentiometer can be used to measure the potential difference.

 A galvanic cell can be constructed by combining two half cells with different
standard electrode potentials.
 The half cell with a more positive Eo value serve as positive terminal
(cathode) where reduction take place.
 The half cell with a more negative Eo value serve as negative terminal
(anode) where oxidation take place.
 A salt bridge connects the two cells and completes the electrical circuit.
 Each half-cell consists of an electrode in an electrolyte solution.
 Requires a conductive solid electrode (metal/graphite) to allow the transfer
of electrons through external circuit.
 The overall reaction that takes place in the galvanic cell is the cell reaction.
 Potential difference is also referred to as electromotive force (emf).
4.2 GALVANIC CELL
Components of Galvanic Cell
a) Half Cell
 A half cell is made by filling a vessel with solution of ion and electrode.
 Example: one half cell consist of a copper electrode immersed in copper
sulfate solution and the other half cell consist of silver electrode immersed
in silver nitrate solution.
 The two-half cell are connected by a salt-bridge.
b) Salt Bridge
 The salt bridge completes the electrical circuit and allows ions to flow
through both half-cells.
 The flow of ions within the salt bridge neutralizes this charge buildup,
allowing reaction to continue.
 A salt bridge contains non-reacting cations and anions, often K+ and NO3-,
dissolved in a gel.
4.2 GALVANIC CELL
 As Cu is oxidized at the anode, Cu2+ ions are formed and enter the solution.
Build up the positive charge in half cell.
 Ag+ ions leave solution to be reduced at the cathode. Build up the negative
charge in half cell.
 The anion NO3- , neutral the excess positive charge from the anode, and K+
neutral the excess negative charge from the cathode.
4.2 GALVANIC CELL
c) Electrode
 Commonly, the anode is made of the metal that is oxidized and the cathode
is made of the same metal as is produced by the reduction.
 However, if the redox reaction involved the oxidation or reduction of an ion
to a different oxidation state, or oxidation or reduction of a gas, inert
electrode is used.
 Inert electrode such as Platinum (Pt) or Graphite (C).
 From the given diagram, since the half-reaction involves reducing the Mn
oxidation state from +7 to +2, thus, we use an electrode that will provide a
surface for the electron transfer without reacting with the MnO4−.
Platinum works
well because it is
extremely
nonreactive and
conducts electricity.
Inert electrode: Pt(s), C(s)

4.2 GALVANIC CELL
IUPAC Cell Notation of Galvanic Cell
 Shorthand description of a voltaic cell

 Electrode | electrolyte || electrolyte | electrode
 Oxidation half-cell on the left, reduction half-cell on the right
 Single | = phase barrier
 if multiple electrolytes in same phase, a comma is used rather than |
 often use an inert electrode
 Double line || = salt bridge
4.2 GALVANIC CELL
Salt
Anode Bridge Cathode  ABC
Anode terminal Anode Cathode terminal

electrolyte
Phase Cathode Phase
boundary electrolyte boundary
EXAMPLE
For the reaction below:
Cr2+ (aq) + Ag+ (aq)  Cr3+ (aq) + Ag (s)
Sketch and label a voltaic cell in which one half-cell has Ag(s) immersed in 1 M
AgNO3, and the other half-cell has a Pt electrode immersed in 1 M Cr(NO3)2 .
Write the two half-equations and cell notation.
SOLUTION
e− → e− →
e− →
e− →
salt
bridge
anode = Pt cathode = Ag
Cr2+,Cr3+ Ag+
ox: Cr2+(aq) → Cr3+(aq) + 1 e− red: Ag+(aq) + 1 e− → Ag(s)
Pt(s) | Cr2+(aq), Cr3+(aq) || Ag+(aq) | Ag(s)

EXAMPLE
Sketch the galvanic cell diagram from the following reactions. Write the cell
notation.
H2(g) + Cu2+(aq) → 2H+ (aq) + Cu(s)
SOLUTION
Oxidation: H2(g) → 2H+ (aq) + 2e-

Reduction: Cu2+(aq) + 2 e− → Cu(s)
SOLUTION
e− → e− →
e− →
e− →
H2
salt
bridge
anode = Pt cathode = Cu
H+ Cu2+
ox: H2(g) → 2H+ (aq) + 2e- red: Cu2+(aq) + 2 e− → Cu(s)
Redox equation: H2(g) + Cu2+(aq) → 2H+ (aq) + Cu(s)
Cell notation: Pt(s) | H2(g) | 2H+ (aq) || Cu2+(aq) | Cu(s)

CHECKPOINT 4
1. Sketch the voltaic cell represented by the following the reaction.

Write the cell notation.
Zn(s)+ Cu2+ (aq)  Zn2+ (aq) + Cu(s)
2. Sketch the voltaic cell represented by the following notation and write
the overall balanced equation for the reaction.
Mn(s)Mn2+(aq) ClO2(g) ClO2-(aq)Pt(s)
4.3 STANDARD ELECTRODE POTENTIAL AND CELL
POTENTIAL
LEARNING OBJECTIVES
•Explain the standard hydrogen electrode as a reference electrode to measure

the electrode potentials of other half-cells.
•Calculate standard reduction potential, E° using standard hydrogen electrode
•Predict the strength of oxidizing and reducing agent using standard reduction
potential, E° values.
•Calculate the standard cell potential E°cell of a galvanic cell.
•Predict spontaneity of a redox reaction using standard reduction potential, E°
POTENTIAL
4.3.1 Standard Electrode Potential
All metals are reducing agents (low IE)- tendency to lose electrons – they
are reducing agent
Mg(s) → Mg2+(aq) + 2e-
Cu(s) → Cu2+(aq) + 2e-
The metal cations have tendency to accept electrons – they are oxidizing
agents
Mg2 +(aq) + 2e- → Mg(s)
Cu2 +(aq) + 2e- → Cu(s)
POTENTIAL

A strip of Mg is immersed in an aqueous solution containing Mg2+ ions (water).
Mg, being a reducing agent, has tendency to lose electrons and goes into
solution as Mg2+ aqueous ion, leaving behind the electrons. This make the
metal negatively charged
Mg(s) → Mg2+(aq) + 2e-
The reverse reaction, where Mg2+ remove electrons from the atoms of the
metal and get deposited as neutral atoms. This make the metal positively
charged
Mg2+(aq) + 2e- → Mg(s)
Photo source: https://www.chemguide.co.uk/physical/redoxeqia/introduction.html
POTENTIAL
• Dynamic equilibrium will be established when the rate at which ions are
leaving the surface is exactly equal to the rate at which they are joining it
again.
• At that point there will be a constant negative charge on the magnesium,

and a constant number of magnesium ions present in the solution around
it.
Mg2+(aq) + 2e- ⇌ Mg(s)
• The position of equilibrium depends on the nature of the metal. For a

reactive metal like Mg, the equilibrium lies more to the LEFT HAND SIDE.
As a result, the Mg strip acquires a net negative charge.
• A potential difference develops between the piece of negatively

charged Mg metal and the solution, thus we called it as the electrode
potential.
POTENTIAL
• For a non-reactive metal like Cu
Cu2+(aq) + 2e- ⇌ Cu(s)
• The equilibrium lies more to the RIGHT HAND-SIDE. As a result, the Cu

electrode acquires a net positive-charged.
• The electrode potential is a measure of the ease of loss of electrons

by a metal. The more negative the electrode potential of a half-cell
the easier it is to lose electrons (oxidation) and the more positive the
electrode, the easier it is for its ion to accept electrons (reduction)
• When the half-cells are connected, the electrons flow from the electrode
with more negative charge (greater potential energy) to the electrode
with more positive charge (less potential energy)
POTENTIAL
• We would conclude that the electrode potential of the magnesium half cell is
more negative than that of the copper half cell.
• It is this difference that provides the driving force that drives electrons
through connecting wire from the magnesium half cell to the copper half
cell. The potential difference between the two half cells is called the cell
potential.
• Cell potential: the maximum potential between the electrodes of a
galvanic cell. Also known as electromotive force (e.m.f.) of the cell, Ecell.
• The electrode potential of half cells depends on several factors
The nature of electrode, temperature (T) , pressure(P) and concentration (M) of
ions in the electrolyte.
• Standard conditions for measuring electrode potential of half-cells,
T is fixed at 25oC, P fixed at 1 atm, M of ion is fixed at 1.00 M
• Under such conditions, the electrode potential is call standard electrode
potential, SEP @ standard reduction potential, SRP– are written in
reduction form with a reversible sign.
POTENTIAL
4.3.2 Standard Hydrogen Electrode (SHE)
• How do we measure the standard electrode potential?

• The standard hydrogen electrode (SHE) is the electrode that was chosen
by IUPAC for comparing electrochemical cell potentials or also known as
reference electrode. The voltage between this electrode and its solution
has been assigned the potential of exactly 0 V.
• We select a standard half-reaction reduction of H+ to H2 under standard
conditions, which SHE reduction potential is arbitrarily fixed at 0.00 V.
 Standard conditions: 1 M acid solution (1M HCl @ 0.5 M H2SO4)
 P at 1 atm H2 gas , T at 25ºC
2H+ (aq) + 2e- ⇌ H2 (g) Eo = 0.00V

POTENTIAL
Measurement of Standard Reduction Potential
Photo source: Chemistry: A Molecular Approach by Tro, Nivaldo J.2008 Pearson education
POTENTIAL
2e-
Eo cell = Eocathode – Eo anode
0.76V = 0.00 V – Eo anode
Eo anode = - 0.76 V
2e-
Eo cell = Eocathode – Eo anode
-0.34 V= 0.00 V – Eo anode
Eo anode = + 0.34 V
Cu2+(aq) + 2e- ⇌ Cu(s) Eo = +0.34V
Zn2+ (aq) + 2e- ⇌ Zn (s) Eo = -0.76V

POTENTIAL
4.3.3 Standard Reduction Potential
• Standard Reduction Potential(SRP) compare the tendency for a particular

reduction half-reaction to occur relative to the reduction of H+ to H2 (SHE)
under standard conditions.
• Half-reactions with a stronger tendency toward reduction than the SHE will
have a + value for E°red
• Half-reactions with a stronger tendency toward oxidation than the SHE will
have a - value for E°red (the more negative value, the more likely substance
to be oxidized and vice versa)
• When two half-cells are connected:
 The one with the larger reduction potential/ more positive reduction potential
will acquire electrons and undergo reduction.
 The half-cell with the lower reduction potential/ more negative reduction
potential will give up electrons and undergo oxidation.
• Cell potential results from the difference in the electrical potentials for each
electrode.
POTENTIAL
Standard Electrode (Reduction) Potentials in Aqueous Solution at 25°C
Cathode (Reduction)
Reduction potential is Half-Reaction
Standard Potential,E° (volts)
been tabulated based on Li+(aq) + e- ⇋ Li(s) -3.04

reference electrode. K+(aq) + e- ⇋ K(s) -2.92
Ca2+(aq) + 2e- ⇋ Ca(s) -2.76
Na+(aq) + e- ⇋ Na(s) -2.71
Mg2+(aq) + 2e- ⇋ Mg(s) -2.38
Al3+(aq) + 3e- ⇋ Al(s) -1.66
2H2O(l) + 2e- ⇋ H2(g) + 2OH-(aq) -0.83
Zn2+(aq) + 2e- ⇋ Zn(s) -0.76
Cr3+(aq) + 3e- ⇋ Cr(s) -0.74
Fe2+(aq) + 2e- ⇋ Fe(s) -0.41
Cd2+(aq) + 2e- ⇋ Cd(s) -0.40
Ni2+(aq) + 2e- ⇋ Ni(s) -0.23
Sn2+(aq) + 2e- ⇋ Sn(s) -0.14
Pb2+(aq) + 2e- ⇋ Pb(s) -0.13
Fe3+(aq) + 3e- ⇋ Fe(s) -0.04
2H+(aq) + 2e- ⇋ H2(g) 0.00
Sn4+(aq) + 2e- ⇋ Sn2+(aq) 0.15
Cu2+(aq) + e- ⇋ Cu+(aq) 0.16
ClO4-(aq) + H2O(l) + 2e- ⇋ ClO3-(aq) + 2OH-(aq) 0.17
AgCl(s) + e- ⇋ Ag(s) + Cl-(aq) 0.22
Cu2+(aq) + 2e- ⇋ Cu(s) 0.34
ClO3-(aq) + H2O(l) + 2e- -> ClO2-(aq) + 2OH-(aq) 0.35
Table source: General Chemistry 9th Edition. Darrell D.Ebbing and Steven D. Gammon. 2009 Cengage Learning.
POTENTIAL
Cathode (Reduction)
Half-Reaction
IO-(aq) + H2O(l) + 2e- ⇋ I-(aq) + 2OH-(aq) 0.49
Cu+(aq) + e- ⇋ Cu(s) 0.52
I2(s) + 2e- ⇋ 2I-(aq) 0.54
ClO2-(aq) + H2O(l) + 2e- ⇋ ClO-(aq) + 2OH-(aq) 0.59
Fe3+(aq) + e- ⇋ Fe2+(aq) 0.77
Hg22+(aq) + 2e- -> 2Hg(l) 0.80
Ag+(aq) + e- ⇋ Ag(s) 0.80
Hg2+(aq) + 2e- -> Hg(l) 0.85
ClO-(aq) + H2O(l) + 2e- ⇋ Cl-(aq) + 2OH-(aq) 0.90
2Hg2+(aq) + 2e- ⇋ Hg22+(aq) 0.90
NO3-(aq) + 4H+(aq) + 3e- ⇋ NO(g) + 2H2O(l) 0.96
Br2(l) + 2e- ⇋ 2Br-(aq) 1.07
O2(g) + 4H+(aq) + 4e- ⇋ 2H2O(l) 1.23
Cr2O72-(aq) + 14H+(aq) + 6e- ⇋ 2Cr3+(aq) + 7H2O(l) 1.33
Cl2(g) + 2e- ⇋ 2Cl-(aq) 1.36
Ce4+(aq) + e- ⇋ Ce3+(aq) 1.44
MnO4-(aq) + 8H+(aq) + 5e- ⇋ Mn2+(aq) + 4H2O(l) 1.49
H2O2(aq) + 2H+(aq) + 2e- ⇋ 2H2O(l) 1.78
Co3+(aq) + e- ⇋ Co2+(aq) 1.82
S2O82-(aq) + 2e- ⇋ 2SO42-(aq) 2.01
O3(g) + 2H+(aq) + 2e- ⇋ O2(g) + H2O(l) 2.07
F2(g) + 2e- ⇋ 2F-(aq) 2.87
POTENTIAL
4.3.4 Strengths of Oxidizing and Reducing Agents
Uses of SRP/SEP to compare the strength of oxidizing agent and reducing

agent
Zn2+(aq) + 2e- ⇌ Zn(s) E°red = -0.76 V
The more positive the E° value, the stronger the oxidizing agent
The more negative E° value , the stronger the reducing agent
The strength of Zn as reducing agent is -0.76 V and the strength of Zn2+ as
oxidizing agent is -0.76 V.* Note that the value used is similar as we are using
reduction potential based on SEP Table – without reversing to the oxidation
equation.
Therefore Zn is a strong reducing agent while Zn2+ is a weak oxidizing agent
Note – on the left side is oxidizing agent, and on the right side is reducing agent
EXAMPLE
Zn2+(aq) + 2e- ⇌ Zn(s) E°red = -0.76 V

Cu2+(aq) + 2e- ⇌ Cu(s) E°red = +0.34 V
Identify which species is the stronger oxidizing agent ?
SOLUTION
Cu2+ is a stronger oxidizing agent because it has more positive potential
value
POTENTIAL
Cathode (Reduction)
Half-Reaction
Li+(aq) + e- ⇋ Li(s) -3.04
K+(aq) + e- ⇋ K(s) -2.92
Ca2+(aq) + 2e- ⇋ Ca(s) -2.76
Weaker oxidizing Stronger
Na+(aq) + e- ⇋ Na(s) -2.71
agent Mg2+(aq) + 2e- ⇋ Mg(s) -2.38
reducing
Al3+(aq) + 3e- ⇋ Al(s) -1.66 agent/ Higher
2H2O(l) + 2e- ⇋ H2(g) + 2OH-(aq) -0.83 tendency to
Zn2+(aq) + 2e- ⇋ Zn(s) -0.76 oxidised
Cr3+(aq) + 3e- ⇋ Cr(s) -0.74
Fe2+(aq) + 2e- ⇋ Fe(s) -0.41
Cd2+(aq) + 2e- ⇋ Cd(s) -0.40
Ni2+(aq) + 2e- ⇋ Ni(s) -0.23
Sn2+(aq) + 2e- ⇋ Sn(s) -0.14
Pb2+(aq) + 2e- ⇋ Pb(s) -0.13
Fe3+(aq) + 3e- ⇋ Fe(s) -0.04
2H+(aq) + 2e- ⇋ H2(g) 0.00
Sn4+(aq) + 2e- ⇋ Sn2+(aq) 0.15
Cu2+(aq) + e- ⇋ Cu+(aq) 0.16
ClO4-(aq) + H2O(l) + 2e- ⇋ ClO3-(aq) + 2OH-(aq) 0.17
AgCl(s) + e- ⇋ Ag(s) + Cl-(aq) 0.22
Cu2+(aq) + 2e- ⇋ Cu(s) 0.34
ClO3-(aq) + H2O(l) + 2e- -> ClO2-(aq) + 2OH-(aq) 0.35
POTENTIAL
Cathode (Reduction)
Half-Reaction
IO-(aq) + H2O(l) + 2e- ⇋ I-(aq) + 2OH-(aq) 0.49
Cu+(aq) + e- ⇋ Cu(s) 0.52
I2(s) + 2e- ⇋ 2I-(aq) 0.54
ClO2-(aq) + H2O(l) + 2e- ⇋ ClO-(aq) + 2OH-(aq) 0.59
Fe3+(aq) + e- ⇋ Fe2+(aq) 0.77
Hg22+(aq) + 2e- -> 2Hg(l) 0.80
Ag+(aq) + e- ⇋ Ag(s) 0.80
Hg2+(aq) + 2e- -> Hg(l) 0.85
ClO-(aq) + H2O(l) + 2e- ⇋ Cl-(aq) + 2OH-(aq) 0.90
2Hg2+(aq) + 2e- ⇋ Hg22+(aq) 0.90
NO3-(aq) + 4H+(aq) + 3e- ⇋ NO(g) + 2H2O(l) 0.96
Br2(l) + 2e- ⇋ 2Br-(aq) 1.07
O2(g) + 4H+(aq) + 4e- ⇋ 2H2O(l) 1.23
Cr2O72-(aq) + 14H+(aq) + 6e- ⇋ 2Cr3+(aq) + 7H2O(l) 1.33
Cl2(g) + 2e- ⇋ 2Cl-(aq) 1.36
Stronger Ce4+(aq) + e- ⇋ Ce3+(aq) 1.44
MnO4-(aq) + 8H+(aq) + 5e- ⇋ Mn2+(aq) + 4H2O(l) 1.49
oxidizing agent/ Weaker
H2O2(aq) + 2H+(aq) + 2e- ⇋ 2H2O(l) 1.78
Higher tendency reducing
Co3+(aq) + e- ⇋ Co2+(aq) 1.82
to reduced S2O82-(aq) + 2e- ⇋ 2SO42-(aq) 2.01
agent
O3(g) + 2H+(aq) + 2e- ⇋ O2(g) + H2O(l) 2.07
F2(g) + 2e- ⇋ 2F-(aq) 2.87
POTENTIAL
Trend down a group of element Group 2A and Group 17
Group 2A Eo/V Group 17 Eo/V

Be2+(aq) + 2e- ⇌ Be(s) -1.85 F2(g) + 2e- ⇌ 2F-(aq) +2.87
Mg2+(aq) + 2e- ⇌ Mg(s) -2.37 Cl2(g) + 2e- ⇌ 2Cl-(aq) +1.36
Ca2+(aq) + 2e- ⇌ Ca(s) -2.87 Br2(l) + 2e- ⇌ 2Br-(aq) +1.07
Sr2+(aq) + 2e- ⇌ Sr(s) -2.89 I2(s) + 2e- ⇌ 2I-(aq) +0.54
Ba2+(aq) + 2e- ⇌ Ba(s) -2.90
Down the group (Be → Ba) the Down the group (F2 → I2) the
strength of reducing agent strength of oxidizing agent
increases. decreases.
CHECKPOINT 5
1. Arrange the following species in order of increasing oxidizing AGENT

strength and reducing AGENT strength
Zn2+(aq) + 2e− ⇌ Zn(s) E°red = −0.76 V
Fe3+(aq) + e− ⇌ Fe2+(aq) E°red = +0.77 V
Cd2+(aq) + 2e− ⇌ Cd(s) E°red = −0.40 V
2. The Eo for several half-cells is given below:
X2+(aq) + 2e− ⇌ X(s) E°red = −0.23 V
Y3+(aq) + 3e− ⇌ Y(s) E°red = +0.57 V
Z2(s) + 2e− ⇌ 2Z-(aq) E°red = −1.05 V
From the above data, how Y, Z2 and X2+ can be concluded?

POTENTIAL
4.3.5 Cell Potential
The maximum potential difference between the electrodes of a voltaic cell is
called the cell potential or electromotive force (emf) of the cell, or Eοcell.
°
Ecell = Ecathode
° °
− Eanode
– Eοcell depends on:
• The composition of the electrodes.

• The concentration of the ions in the half-cells.
• The temperature and pressure.
– A positive Eοcell indicates a spontaneous reaction.

EXAMPLE
Calculating Cell Potentials under standard conditions
Calculate the standard cell potential of the following voltaic cell at 25°C using
standard electrode potentials.
Al3+/Al Eo = -1.66 V
Fe2+/Fe Eo = -0.41 V
SOLUTION Al(s) | Al3+(aq) || Fe2+(aq) | Fe(s)

°
Ecell = Ecathode
° °
− Eanode
°
Ecell = EFe
°
− E Al°
= − 0.41 V − ( − 1.66 V )
= 1.25 V
POTENTIAL
4.3.6 Spontaneity of Redox Reaction under Standard Conditions
• Spontaneity of reaction also can be determined by looking at the cell

potential.
• Positive cell potential indicates the redox reaction is spontaneous while
negative cell potential indicates non-spontaneous.
Cu2+(aq) + 2 e− ⇌ Cu(s) E°red = +0.34 V

Zn2+(aq) + 2 e− ⇌ Zn(s) E°red = −0.76 V
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Cu(s) + Zn2+(aq) → Cu2+(aq) + Zn(s)

spontaneous non-spontaneous
Eocell = (+0.34V) – ( −0.76V) Eocell = (−0.76V) – (+0.34V)

= +1.10V positive value = −1.10V negative value
EXAMPLE
Consider the following reaction:
Zn2+ ( aq ) + 2Fe2+ ( aq ) → Zn ( s ) + 2Fe3+ ( aq )

Does the reaction go spontaneously as written, under standard conditions?
SOLUTION
The corresponding standard electrode potentials are:
Zn2+/Zn Eo = -0.76 V, Fe3+/Fe2+ Eo = +0.77 V
In this reaction, Zn2+ is a weak oxidizing agent and Fe2+ is a weak reducing agent.
The reaction cannot occur.
Eocell = ( −0.76V) – (+0.77V)
= -1.53V positive value
The reaction is nonspontaneous as written.

@ spontaneous reaction in reverse direction
EXAMPLE
Predict the reaction that will occur when both Ni and Fe are added to a
solution that contains both Ni2+ and Fe2+, each at 1 M concentration.
From SRP table, we obtain:
Ni2+(aq) + 2e- ⇌ Ni(s)
Fe2+(aq) + 2e- ⇌ Fe(s)
Because -0.44 V < -0.25 V, Fe2+/Fe pair will undergo oxidation.
SOLUTION
Half equation at cathode: Ni2+(aq) + 2e- → Ni(s)
half equation at anode: Fe(s) → Fe2+(aq) + 2e-
overall: Ni2+(aq) + Fe(s) ➝ Ni(s) + Fe2+(aq)
°
Ecell = Ecathode
° °
− Eanode = EºNi - EºFe
= -0.25 V – (-0.44 V)
= + 0.19 V
Positive value indicates a spontaneous reaction.
CHECKPOINT 6
1. Calculate the e.m.f. and state whether the reaction to occur

spontaneously in forward reaction.
a) Ni(s) + Zn2+(aq) → Ni2+(aq) + Zn(s)
b) Ni(s) + Pb2+(aq) → Ni2+(aq) + Pb(s)
c) 2Al(s) + 3Pb2+(aq) → 2Al3+(aq) + 3Pb (s)
2. Given, 2Ce4+ + Co → 2Ce3+ + Co2+ Eocell = 1.89V. The standard

reduction potential for Co2+ is -0.28V. Determine the standard reduction
potential for Ce4+ to Ce3+ .
4.4 NON-STANDARD CELL POTENTIAL
LEARNING OBJECTIVES
• Calculate the non-standard cell potential, Ecell of a cell using Nernst

equation.
When the concentration ions of electrolyte is changed or other factors such as

pressure, pH and temperature also changes during course of reaction, thus the
conditions is no longer as standard, and the cell potential is also changed.
The effect of concentration on the cell potential of a Cell

• It is possible to get a spontaneous reaction when the oxidation and reduction
reactions are the same, as long as the electrolyte concentrations are different
• For same electrolyte, electrons will flow from the electrode in the less
concentrated solution to the electrode in the more concentrated solution
a) anode - oxidation of the electrode in the less concentrated solution
b) cathode - reduction of the solution ions at the electrode in the more
concentrated solution
Cu(s) | Cu2+(aq) || Cu(aq) | Cu(s)
When the cell concentrations are equal
• no difference in energy between the half-
cells
• no electrons flow
When the cell concentrations are different:

• electrons flow from the side with the less
concentrated solution (anode) to the side with the
more concentrated solution (cathode)
LESS  MORE
Cu(s)+ Cu2+(aq) (2.0 M) ⇌ Cu2+(aq) (0.01 M)+ Cu(s)
The Le Chatelier’s principle is used to predict
qualitatively how the electrode potential of a half cell
changes with a change in concentration. Example
Cu2+(aq) + 2e- ⇌ Cu(s) Eo = +0.34 V
As the [Cu2+] is increased, the equilibrium will

shift to the right.
Make more Cu2+ ions will accept the electrons

from the copper electrode and get deposited
as copper atoms. As a result, the copper
electrode becomes more positive.
When concentration of the Cu2+ is decreased,

the equilibrium lies to the left. More copper
atoms will remove the electrons and
dissolved to form more Cu2+, leaving behind
their electrons. As a result, the copper
electrode becomes more negatively-charged.
EXAMPLE
Given the following half cell
Cl2 (g) + 2e- ⇌ 2Cl-(aq) Eo = +1.36 V
Predict qualitatively how the electrode potential will change on

increasing the Cl- concentration.
ANSWER
[Cl-] is increased, the equilibrium lies to the left, more Cl- will get
oxidized to Cl2, as a result the platinum electrode becomes more
negatively charge and the electrode potential decreases (Eo becomes
less positive).
CHECKPOINT 7
Given the following half cell
Fe3+ (aq) + e- ⇌ Fe2+(aq) Eo = +0.77 V
How to increase the electrode potential?

The effect of concentration on the E.M.F of the Cell

When ion concentrations are not 1 M for different electrolyte.
The effect of concentration on the E.M.F of the Cell
Consider the reaction below
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Eocell = 1.10V
Cu2+(aq, 1.0M) + 2 e− ⇌ Cu(s) E°= +0.34V

Zn2+(aq, 1.0M) + 2 e− ⇌Zn(s) E°= -0.76V
If the concentration of Cu2+ is increased, the electrode potential of the

copper half-cell will become more positive, hence the e.m.f. > 1.10V
The above reaction will be displaced towards the right.
Similarly, if the concentration of Cu2+ is decreased, the reaction will be

displaced towards the left. This will make the Ecell more negative, e.m.f. <
1.10V
Hence, when the [ reactant] ion increases, the e.m.f of the cell will
increase or when the [product] ion increase, the e.m.f of the cell will
decrease
CHECKPOINT 8
1. Consider the cell below
Pt(s)| H2(g)| H+(aq) ΙΙ Fe3+(aq), Fe2+(aq) | Pt(s)
Fe3+/Fe2+ Eo = +0.77V
a) Calculate the standard cell potential of the cell under standard condition.
b) Show the direction of electrons.
c) Predict how the potential of the cell will change if the concentration of
Fe3+(aq) is increased.
d) Suggest a half-cell which when used to replace the Fe3+/Fe2+ half cell will
reverse the flow of electrons in the standard hydrogen electrode.
CHECKPOINT 8
2. Consider the cell below

Al(s)  Al3+(aq)  Cu2+(aq) Cu(s)
Al3+/Al Eo = -1.66 V
Cu2+/Cu Eo = +0.34 V
a) Calculate the standard e.m.f. of the cell under standard condition.

b) Write the overall cell reaction
c) Predict how the e.m.f. of the cell will change if the concentration of
i) Al3+(aq) is decreased and ii) concentration of Cu2+(aq) is increased.
4.4.1 Nernst Equation

The quantitative relationship between electrode potential and concentration of
aqueous ions (as well as temperature )is given by the Nernst equation
Where:
n = no. of moles of electrons
[product]x The oxidized form

Q= The reduced form
[reactant]y
Note: Reaction quotient (Q) using molar concentrations for ions and partial pressure for
gases.
4.4.1 Nernst Equation
Q values gives indication of concentration of reactant and product as follow:
When [Cu2+] increased, Q < 1 and thus log Q < 0, so Ecell > E°cell
When [Cu2+] = [Zn2+], Q = 1 and thus log Q = 0, so Ecell = E°cell (at equilibrium,
log K)
When [Cu2+] decreased, Q >1 and thus , log Q > 0, so Ecell < E°cell
Note: In heterogeneous systems, which involve solids, do not include solid in Nernst
Equation ( for Q)
EXAMPLE
Consider a galvanic cell involving the following half-reactions:
Ni2+(aq) + 2e- ⇌ Ni(s)

Cr3+(aq) + 3e- ⇌ Cr(s)
Calculate the cell potential when [Ni2+] = 1.0 × 10-4 M and [Cr3+] = 2.0 × 10-3 M.
SOLUTION
Because the concentrations are not 1 M, use the Nernst equation.
Because -0.74 V < -0.25 V, the Cr3+/Cr pair will undergo oxidation.
Ni2+(aq) + 2e- → Ni(s)
Cr(s) → Cr3+(aq) + 3e-
Then balance the number of electrons and add them together:
3Ni2+(aq) + 6e- → 3Ni(s)
2Cr(s) → 2Cr3+ (aq) + 6e-
3Ni2+ (aq) + 2Cr(s) ⇌ 3Ni(s) + 2Cr3+ (aq)
Cont. SOLUTION
Then the E°cell of the reaction
3Ni2+ (aq) + 2Cr(s) → 3Ni(s) + 2Cr3+ (aq)
can be determined as:
°
Ecell = Ecathode
° °
− Eanode
= EºNi - EºCr
= -0.25 V – (-0.74 V)
= + 0.49 V
We next write down the Nernst equation:
o 0.0592
Ecell = Ecell - log Q
n
=E o
-
[ ]
0.0592
log
Cr 3+
2
cell
6 [ ] Ni2+
3
= 0.49 V -
0.0592
log
[2.0 ×10 ] -3 2
6 [1.0 ×10 ] -4 3
= 0.49 V - 0.0651 V
= 0.42 V
CHECKPOINT 9
1. A voltaic cell consists of Ag+/Ag half cell with concentration 0.10 M and the
other half-cell of Ag+/Ag with concentration 10.0 M at 25oC. EoAg+/Ag = +0.80 V
a. Determine the direction of electrons.
b. Calculate the initial cell potential.
2. Consider the following cell.

Pt(s) ⎢Cl2(g, 1.0 atm)⎪Cl-(0.10 M) ⎢⎢ H+(1.0 M), MnO4- (0.20 M), Mn2+ (0.10 M) ⎪Pt(s)
a. Calculate the Ecell and determine whether the cell reaction will proceed
spontaneously.
b. Calculate the Ecell if the concentration of Cl- is replaced with 1.0 x 10-3 M
determine whether the cell reaction will proceed spontaneously.
Given
MnO4-(aq) + 8H+(aq) + 5e- ⇌ Mn2+(aq) + 4H2O(l) Eo = +1.52 V
Cl2(g) + 2e- ⇌ 2Cl-(aq) Eo = +1.36 V
CHECKPOINT 9
3. A voltaic cell consists of a Zn2+/Zn half cell and Ni2+/Ni half cell at 25oC. The
initial concentrations of Ni2+ and Zn2+ are 1.50 M and 0.1 M respectively.
Zn2+/Zn Eo = -0.76 V Ni2+/Ni Eo = -0.25 V
a. Calculate the initial cell potential?
b. Determine the cell potential when the concentration of Ni2+ has fallen to 0.5
M?
c. What are the ratio for concentrations of Ni2+ and Zn2+ when the cell potential
falls to 0.45 V? Calculate the concentration for each ion.
4.5 ELECTROLYTIC CELL AND ITS APPLICATIONS
LEARNING OBJECTIVES
• Explain the components and operation of an electrolytic cell.

• Predict the products formed during electrolysis using standard reduction
potential values.
• Explain the use of electrolysis in the extraction of aluminium from bauxite.
4.5.1 Electrolytic Cell

An electrochemical cell in which an external energy source drives an otherwise
nonspontaneous reaction.
The process of producing a chemical change in an electrolytic cell is called

electrolysis. Many important substances are produced commercially by
electrolysis. For example, aluminum and chlorine.
• The DC source serves as an ‘ electron

pump ’ , pulling electrons away from one
electrode and pushing them through the
external wiring onto the other electrode.
• Because of the nature of the chemical
change in an electrolysis cell, the positive
electrode becomes the anode, to which the
anions move.
• The negative electrode is the cathode, to
which the cations move.
Photo source: Chemistry 3rd Edition. Blackman,Bottle, Schmid, Mocerino & Wille.2016. John Wiley & Sons Australia.
4.5.1 Electrolytic Cell
Comparison between electrolytic and galvanic cells
ELECTROLYTIC CELL GALVANIC CELL

• Cathode is negatively charged • Cathode is positively charged
(reduction) (reduction)
• Anode is positively charged • Anode is negatively charged
(oxidation) (oxidation)
• Electrons flow from the cathode to • Electrons flow from the anode to
anode cathode
• Non-spontaneous redox reaction • Spontaneous redox reaction
4.5.2 Factors Affecting Products of Electrolysis
1.The standard electrode potential of the competing species

• The stronger an oxidizing agent, the greater is its tendency to accept
electrons - the ease to be discharged at the cathode (@ species
with more positive Eo values).
e.g Cu2+(aq) + 2e- ⇌ Cu(s) Eo = +0.34V
Ag+(aq) + e- ⇌ Ag(s) Eo = +0.80V
2H2O(l) + 2e- ⇌ H2(g) + 2OH-(aq) Eo = -0.83V
• Ag+ will get reduced first.
• The stronger the reducing agent, the greater is its tendency to lose
electrons - the ease to be discharged at anode (@ species with
more negative Eo values).
e.g Cl2(g) + 2e- ⇌ 2Cl-(aq) Eo = +1.36V
I2(s) + 2e- ⇌ 2I-(aq) Eo = +0.54V
O2(g) + 4H+(aq) +4e- ⇌ 2H2O(l) Eo = +1.23V
• I- will get oxidized first.
2. Concentration of ions in electrolytes

e.g. Cu2+(aq) + 2e- ⇌ Cu(s) Eo = +0.34V
Ag+(aq) + e- ⇌ Ag(s) Eo = +0.80V
Under standard conditions (1 M), the Ag+ will be discharged first at cathode.
However, if we increase the concentration of Cu2+, the electrode potential also
increase. At high enough concentration, the electrode potential of the Cu2+/Cu
half cell can become more positive than +0.80V. Then, it will be discharged
instead of Ag+.
e.g Cl2(s) + 2e- ⇌ 2Cl-(aq) Eo = +1.36V
O2(g) + 4H+(aq) +4e- ⇌ 2H2O(l) Eo = +1.23V
If we increase the concentration of Cl-, (concentrated NaCl) the electrode
potential also decrease. At high enough concentration, the electrode potential
of the Cl2/Cl- half cell can become less positive than +1.23V then, it will be
discharged instead of H2O.
Note: if the difference in the standard electrode potentials of the two competing species is
too large, or species is unstable in water then concentration is no longer an important
factor.
3. Type of electrodes
e.g. in the electrolysis of concentrated NaCl using platinum cathode, hydrogen
gas is liberated.
If cathode changed to mercury, sodium will be formed instead. This is due to
overpotential of hydrogen gas at the mercury electrode. Sodium react with
mercury to form amalgam which is stable in water.
Hg(l)
Na+(aq) + e- → Na/Hg
e.g. in the electrolysis of aqueous copper(II) sulphate using platinum anode,

oxygen is liberated.
If anode changed to copper electrode, the copper anode will be dissolved and
no oxygen gas is liberated.
Notes: Overpotential is the difference between the theoretical cell voltage and the actual voltage that is necessary to
cause electrolysis
4.5.3 Electrolysis of Molten Salt

• The compound must be in molten (liquid) state
• Use inert electrodes ( Graphite etc)
• Cations are reduced at the cathode to metal element
• Anions oxidized at anode to nonmetal element
Electrolysis of molten sodium chloride (single molten ionic compound)
Very straight forward

because consists of one
type of cation and anion
only.
Photo source: General Chemistry 9th Edition. Darrell D.Ebbing and Steven D. Gammon. 2009 Cengage Learning.
4.5.4 Electrolysis of Mixtures of Molten Ionic Salts
When there are more than one cation is present, the cation that is easiest to
reduce will be reduced first at the cathode.
 The reduction half-reaction with the most positive E°red will be reduced at
the cathode
When more than one anion is present, the anion that is easiest to oxidize will be
oxidized first at the anode.
 The reduction half-reaction with the most negative E°red will be oxidized at
the anode
EXAMPLE
Predict the product of electrolysis of a mixture of molten AlBr3 (l) and
MgBr2(l).
SOLUTION
AlBr3(l) → Al3+(l) + 3Br-(l)
MgBr2(l) → Mg2+(l) + 2Br-(l)
Anode: only one type of anion (Br-) undergoes oxidation to produce Br2 gas
Half reaction at anode : 2 Br−(l) → Br2(g) + 2 e−
Cathode: two cations Al3+ and Mg2+ attracted to cathode. Which of the two
cations is reduced?
Al3+(aq) + 3 e− ⇌ Al(s) E°= −1.66 V
Mg2+(aq) + 2 e− ⇌ Mg(s) E°= −2.37 V
because the reduction potential, E° of Al3+ has a less negative (more positive),
thus it is most easily reduced is reduced first.
Half reaction at cathode: Al3+(l) + 3 e− → Al(s)
EXAMPLE
Predict the product of electrolysis of a mixture of molten NaCl (l) and NaBr(l).
SOLUTION
NaCl(l) → Na+(l) + Cl-(l)
NaBr(l) → Na2+(l) + Br-(l)
Anode: two anions Cl- and Br- attracted to anode. Which of the two anions is
oxidized?
Cl2(g) + 2e− ⇌ 2Cl-(aq) E°= +1.36 V
Br2(l) + 2 e− ⇌ 2Br-(aq) E°= +1.09 V
Because the reduction potential, Eo of Br- has less positive (more negative),
thus it is most easily oxidized is oxidized first.
Half reaction at anode : 2 Br−(l) → Br2(g) + 2 e−
Cathode: one cation Na+ attracted to cathode undergoes reduction to

produce solid sodium
Half reaction at cathode: Na+(l) + e− → Na(s)

CHECKPOINT 10
1. Predict the product formed at anode for an aqueous solution of sodium

fluoride with concentration
a) diluted.
b) very concentrated.
Explain why
Given F2(g) + 2e- ⇌ 2F-(aq) Eo = +2.87V
O2(g) + 4H+(aq) +4e- ⇌ 2H2O(l) Eo = +1.23V
2. Predict the product(s) formed at cathode and anode in the electrolysis of

a molten mixture salt between CaCl2 and MgI2.
Given Cl2(g) + 2e- ⇌ 2Cl-(aq) Eo = +1.36V

l2(s) + 2e- ⇌ 2l-(aq) Eo = +0.54V
Ca2+(aq) + 2e- ⇌ Ca(s) Eo = -2.76V
Mg2+(aq) + 2e- ⇌ Mg(s) Eo = -2.37V
4.5.4 Electrolysis of Aqueous Solution

Electrolysis of water
Water is a weak electrolyte and not possible for electrolysis due to the conc. of
H+ (10-7 M). Thus, water need to be acidified or add small amount of Na2SO4,
the electrolysis is possible.
O2(g) + 4H+(aq) +4e- ⇌ 2H2O(l) Eo = +1.23V
2H2O(l) + 2e- ⇌ H2(g) + 2OH-(aq) Eo = -0.83V
Oxidation (Anode)
Oxygen release
2H2O(l) → O2(g) + 4H+(aq) +4e-
Reduction (Cathode)
Hydrogen release
2H2O(l) + 2e- → H2(g) + 2OH-(aq)
Overall reaction: 2 H2O(l) → 2 H2(g) + O2(g)


• In aqueous solutions, the possible reactions of water must also be included.
2H2O(l) → O2(g) + 4H+(aq) +4e-
2H2O(l) + 2e- → H2(g) + 2OH-(aq)
• First, examine the possible oxidation reactions. The one with the less positive
E° value will occur. (E° value from SRP table without changing the reaction)
• Next examine the possible reduction reactions. The one with the more
positive E° value will occur.
EXAMPLE
Electrolysis of a potassium sulfate solution
At cathode, competing reactions are:

K+(aq) + e- ⇌ K(s) Eº = -2.92 V
2H2O(l) + 2e- ⇌ H2(g) + 2OH-(aq) Eº = -0.83 V
Thus, H2 gas is produced
At anode, possible competing reactions are:

S2O82-(aq) + 2e- ⇌ 2SO42-(aq) Eº = +2.01 V
4H+(aq) + O2(g) +4e- ⇌ 2H2O(l) Eº = +1.23 V
Thus O2 gas is produced.

2H2O(l) → 4H+(aq) + O2(g) +4e-
Photo source: Chemistry 3rd Edition. Blackman,Bottle, Schmid, Mocerino & Wille.2016. John Wiley & Sons Australia.
EXAMPLE
An aqueous solution of 0.50 M ZnSO4 and 0.50 M NiSO4 undergoes

electrolysis. Based on reduction potentials, what products are expected to be
observed at the electrode?
SOLUTIONS
At the cathode
Ni2+(aq) + 2e- ⇌ Ni(s) E0 Ni2+/Ni = -0.25 V
Zn2+(aq) + 2e- ⇌ Zn(s) E0 Zn2+/Zn = -0.76 V
2H2O(l) + 2e- ⇌ H2(g) + 2OH-(aq) Eº = -0.83 V
At the anode
S2O82-(aq) + 2e- ⇌ 2SO42-(aq) Eº = +2.01 V
4H+(aq) + O2(g) +4e- ⇌ 2H2O(l) Eº = +1.23 V
This answer is based on the more positive reduction potential (Eº value )
will have tendency to undergo reduction and the less positive reduction
potential (Eº value ) will have tendency to undergo oxidation.
Below is a set of rules that can be used to predict the outcomes of electrolysis
reactions in aqueous solution (using inert electrode)
1. Identify all cations and anions in the system. In aqueos solution, we also
have H+ and OH-.
2. The product of electrolysis at the anode is always O2 except if the
electrolytes contains high concentrate ions of Cl-, Br- and I- ions.
The, F-, SO42-, NO3-, CO32- ions never discharged.
3. During electrolysis of aqueous solutions, reactive metals, such as Na or K
are never produced at the cathode. If the cations come from a metal (Group
1A and 2A) that has a less positive reduction potential than water, H2 will be
liberated at the cathode. If the cations (Cu2+, Ag+, Au3+) come from a metal
that has a more positive reduction potential than water, then the metal will
be deposited at cathode.
4. Identify the cations and anions that remain in the solution after electrolysis.
5. Summarise all reactions in 1-4 to obtain the full reaction.
To summarize the best way to choose redox reaction that occur at each
electrode respectively:
CATHODE
The half-reaction with the bigger (more positive) reduction potential occurs
more easily as an reduction.
ANODE
The half-reaction with the smaller (less positive) reduction potential
occurs more easily as an oxidation.
Or
the half-reaction with the larger (less negative) oxidation potential occurs
more easily as an oxidation.
CHECKPOINT 11
1. In the electrolysis of an aqueous solution of sodium chloride solutions,

predict the products formed at each electrode.
2. In the electrolysis of a mixture aqueous solution of tin(II) nitrate and

copper(II) iodide solutions, predict the products formed at each
electrode.
4.5.5 Application of Electrolysis: Extraction of Aluminium From Bauxite
(Positive anodes) graphite

graphite
+ +
Steel case
- Al2O3 Al2O3
-
Al2O3
Al2O3 Al2O3
(Negative
anodes)graphite
-
Molten aluminium collect at the

bottom
When the battery is turned on and electricity flows, the aluminium forms at the
negative cathode and sinks to the bottom of the tank where is tapped off as a
pure liquid metal. Oxygen forms at the positive anodes. The oxygen reacts
with the carbon of the graphite, forming carbon dioxide. The positive anode
therefore burns away, and needs replacing regularly.
4.5.5 Application of Electrolysis: Extraction of Aluminium From Bauxite
Cathode Anode
• The aluminium ions from molten • The oxygen react with carbon to
aluminium oxide- cryolite solution make carbon dioxide, CO2
are reduced • The oxygen ions are oxidised
Al3+(l) + 3e- → Al(l) 2O2-(l) → O2 (g) + 4e-
Economic considerations of aluminium extraction

• Electrolysis process is more cost effective than carbon reduction in extracting
aluminium from bauxite
• But still extracting aluminium is expensive because it uses huge amounts of
electricity
• Energy and materials cost in constantly replacing the anodes

Chem Topic 4

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TOPIC 4

4.1 Redox Reactions

Student should be able to:

4.1.1 Redox Reaction and Oxidation State

4.1.1 Redox Reaction and Oxidation State

 Take place in voltaic cell  In electrolytic cell by addition of

Chemical Electrical Electrical Chemical

 Eg: galvanic cell  Eg: electrolysis

Picture taken from https://chem.libretexts.org/Textbook_Maps/Analytical_Chemistry/Supplemental_Modules_(Analytical_Chemistry)/Electrochemistry/Voltaic_Cells and https://byjus.com/physics/electrolysis-and-electroplating

4.1.1 Redox Reaction and Oxidation State

 An element loses electron  An element gains electron

 Oxidation number of element  Oxidation number of element

 The element is known as reducing  The element is known as oxidizing

 A compound adds oxygen &  A compound loses oxygen &

 A half-equation has electrons as  A half-equation has electrons as

 Eg: Cr2+(aq) Cr3+(aq)+ e-  Eg: Ag+(aq) + e-  Ag (s)

4.1.1 Redox Reaction and Oxidation State

 Oxidation numbers also called as oxidation state.

4.1.1 Redox Reaction and Oxidation State

The 8 rules in assigning the oxidation states

4.1.1 Redox Reaction and Oxidation State

4.1.1 Redox Reaction and Oxidation State

4.1.1 Redox Reaction and Oxidation State

b) Hydrogen + metal → ionic hydride (a binary compound)

4.1.1 Redox Reaction and Oxidation State

c) The oxidation number of Oxygen is +2 when combine with a

Fe2+ (aq) + MnO4- (aq)  Fe3+ (aq) + Mn2+ (aq)

i) Determine the oxidation numbers of Mn in MnO4-

4.1.2 Balancing Redox Equations

 Many redox reactions take place in aqueous solution.

Balance the following redox equation:

This redox equation consists of two half-equations:

Note: all steps above is called as skeleton equation

4.1.2 Balancing Redox Equations

Redox reactions in acidic and basic solution:

4.1.2 Balancing Redox Equations

Balancing oxidation-reduction equations in acidic medium:

Consider this equation

Zn(s ) + NO3 − (aq ) → Zn2+ (aq ) + NH4+ (aq )

4.1.2 Balancing Redox Equations

Zn(s ) → Zn2+ (aq ) oxidation

Zn(s ) → Zn2+ (aq ) + 2e − (oxidation half-reaction)

4.1.2 Balancing Redox Equations

a. Balance other atoms first (balance N atoms first)

c. Balance H atoms by adding H+ to the side of equation

4.1.2 Balancing Redox Equations

4.1.2 Balancing Redox Equations

a. Multiply each half-equation by a factor so that each has the same

4.1.2 Balancing Redox Equations

4Zn (s)  4Zn2+ (aq) + 8e- oxidation

Indicates the redox reaction

4.1.2 Balancing Redox Equations

Balancing oxidation-reduction equations in basic medium:

Consider the same equation;

Zn(s ) + NO3 − (aq ) → Zn2+ (aq ) + NH4+ (aq )

4.1.2 Balancing Redox Equations

NO3-(aq) + 10 H+ (aq)  NH4+ (aq) + 3H2O (l)

NO3-(aq)+ 10H+(aq) + 10OH-(aq)  NH4+ (aq) + 3H2O (l) + 10OH- (aq)

4.1.2 Balancing Redox Equations

4.1.2 Balancing Redox Equations

Continue Step 4 and Step 5 as in acidic solution;

4.1.2 Balancing Redox Equations

a. Multiply each half-equation by a factor so that each has the same

4.1.2 Balancing Redox Equations